CA1098647A - Coordination complexes as catalysts - Google Patents

Abstract

ABSTRACT OF THE INVENTION

A process for producing polyester and co-polyester, useful for making films and fibers, by the polycondensation of dicarboxylic acids and aliphatic glycols using coordinations complexes of metal halides and silicon compounds as catalysts.

Description

'7 BAC~GRO~ID OF T ~

The production of polyesters and copolyesters of dicarboxylic acids and aliphatic glycols has been carried out commercially for many decadesO Among the earliest disclosures relating to this technology is the disclosure in U.S. 2,465,319, issued March 22, 194~.
Since this disclosure many variations have been made in the process and many catalysts have been discovered and patented. On December 8, 1970, there issued U~S. 3,5~6,179, which is directed to the use of compounds containing both the sillcon and phosphorus atoms in the molecule as catalysts.
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It has now been found that coordination complexes of a metal halide and a silicon compound, as hereinafter defined, are excellent polyesterification catalyst complexes for the production of polyesters and copolyesters useful fox making films, fibers and other shaped articles.
~ DESCRIPTION OF THE_INVENTIO~

; 20 In the production of polyesters and copolyesters the reaction is generally considered a dual or two stage ; reaction. In the ~irst stage esterification or trans-es~terification occurs and in the second stage polyconden-sation occurs. This invention is concerned with novel polyesterification catalyst compositions and processes for producin~ pol~esters.
The nove~ catalyst compositions of this invention are~coordination complexes o (A) a metal halide and (B) a silicon compound, as hereinafter more :
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fully defined. The use of our catalyst complexes or compositions results in a shorter reaction period, and the production of polyesters and copolyesters of high - degrees of polycondensation that are characterized by - high melting point, high elongation at break, good tensile strength, high degree of whiteness, and a good stability to heat and light.
The first stage esterification or trans-esterification reaction is carried out in the traditional manner by heating the mixture at from about 150C. to about 270~C, preferably from about 175C. to about 250C.
During this stage any of the well known esterification or transesterification catalysts can be used, illustrative thereof one can mention zinc acetate, manganese acetate, cobaltous acetate, æinc succinate, zinc borate, magnesium methoxide, sodium methoxide, cadmium for~ate, and the like.
The concentration thereof is that conventionally used, namely from about 0.001 ~o about one percent by weight, based on the weight of dicarboxylic acid compound charged.
It is preferably from about 0.005 to about 0.5 percent by weight nnd more preferably from about 0.01 to about 0.2 percent by weight.
In the second stageJ or the polycondensation, the novel coordination complex catalysts of this invention are useful, These novel eoordination complex catalysts comprise two essential components. The first component is a metal halide and the second component is one or more of the hereinaEter defined silicon compounds.
e metal halides used to produce the coordina-:: :
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: ~: : : , tion complexes useful as catalysts are the halides of the metals ti~aniu~, zirconium, zinc, germanium, tin, lead, antimony and bismuth. Illustrative of suitable metal halides one can include the di-, tri~ and tetra- bromides, chlorides, fluorides and iodides of titanium and zirconium;
the di- bromides, chlorides, fluorides and iodides of zinc;
the di- and tetra~ bromides, chlorides, fluorides and iodides of germanium, tin and lead including the mixed bromide-chlorides, bromide-iodides and chloride-iodides of tin; the tri- and penta- bromides, chlorides, fluorides and iodides of antimony; and the tri- and tetra~ bromides, chlorides, fluorides and iodides of bismuth~ These metal halides are well known to the average chemist and are fully enumera~ed in chemical handbooks to the extent that specîfic naming thereof is not necessary herein to enable one skilled in the art to know chemical names of the specific metal halides per se; see the Handbook of Chemistry and Physics, Chemical ~ubber Publishing Co., publisher.
In producing the coordination complexes useful as catalysts, the molar ratio of metal halide to silicon compound in the coordination complex can vary from about 1:0.5 tc about 1:10; preferably from about 1:1 to about 1:7, and most pre~erably from about 1:1 to about 1:2.
In the polycondensation reaction the coordin-ation catalyst complex is used at a concentration of from 0.01 to 0.2 weight percent, or higher, based on the weight o~ d:icarboxylic acid compound charged, preferably from 0.02 to 0.06 weight percent. Any catalytically effective concentration can be employed. As used in this application the term "dicarboxylic acid compound" means ~ ~ .
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both the free dicarboxylic acids and the esters thereof.
The dicarboxylic acid compounds used in the production of polyesters and copolyesters are well known to those skilled in the art cmd illustratively include terephthalic acid, isoterephthalic acid, p,p'-diphenyl-dicarboxylic acid, p,p'-dicarboxydiphenyl ethane, p,p'-dicarboxydiphenyl hexane, p,p'-dicarboxydiphenyl ether, p,p'-dicarboxyphenoxy ethane, and the like, and the di-alkyl esters thereof that contain from 1 to about 5 carbon atoms in the alkyl groups thereof.
Suitable aliphatic glvcols ~or the production of polyesters and copolyesters are the acyclic and ali-cyclic aliphatic glycols having from 2 to lO carbon atoms, especially those represented by the general formula HO(CH2)pOH, wherein p is an integer having a value of from

2 to abaut 10, such as ethylene glycol, trimethvlene glycol, tetramethylene glycol, pentamethylene glycol, decamethvlene glycol, and the like.
Other known suitable aliphatic glycols incIude 1,4-cyclohexanedimethanol, 3-ethyl-1,5-pe~tanediol, 1,~-xylylene glycol, 2,2,4,4-tetramethyl-1,3-cyclohutanediol, and the like. One can also have present a hydroxvl-carboxyl compound such as 4-hydroxybenzoic acid, 4-hydroxy-ethoxybenzoic acid, or any of the other hvdroxylcarboxyl compounds known as useful to those skilled in the art.
It is also known that mixtures of the above dicarboxylic acLd compounds or aliphatic glycols can be used and that a minor amount of the dicarboxylic acid component, generally up to about 10 mole percent, can be replaced by other acids or modifiers such as adipic acid, ~ 5.
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sebacic acid, or the esters thereof, or with a modifier that imparts improved dveability to the pol~Jmers. In addition one can also include pi~nents, delusterants or optical brighteners bv the kno~n procedures and in the known amounts.
The ~olycondensation reaction is generally carried out at a temperature of from about 225C. to about 325C, preferably from about 250C. to about 290~C.
at reduced pressure and under an inert atmosphere. These traditional reaction conditions are well known to those skilled in the art.
The silicon compounds that are used in con-Junction with the metal halide to produce the coordination complex catalyst of this invention are represented by the following generic formulas:

R
- (I) w-(coocn~I2n)m-si-R
R' Me Me .
~ 20 (II) Z-Si-0-Si-W
.
; ~ O
z-si-o-si-~ :
Me Me Me 1 rl~
(III)~ R"'O -sio ~rsio - _ R~ or ~ Me I _Me ~~: : x y ::

:~ :
^:, . . - ,.: . , (IV) QCH2CH2SlR3**
wherein W is CH2=C~- or (R*o)2PcH2cHy- ;
o X is hvdrogen or methyl and is methyl only when m is one;
R* is alkyl or haloalkyl having from 1 to 4 carbon atoms;
R** is methyl, ethyl, butyl, ace~oxy, methoxy, ethoxy or butoxy;
R is methyl, ethyl, butyl, nethoxy, ethoxy, butoxy, or trimethylsiloxy;
R' is methyl, methoxy, ethoxy, butoxy or trimethylsiloxy;
: R" is methoxy, ethoxy, butoxy, trimethyl-siloxy or vinyld~methylsiloxv;
R"' is methyl, ethyl, butyl or trimethylsilyl;
Me is methyl;
: ~. is methyl or l~;
Q is an ~C2CH2~ 2cH2c~2~HcH2-J NC-, HS- or HSCH2CH2S- group;
n is an integer having a value of from 2 to 5;
n is aD integer having a value of zero or one;
x is~an~integer having a value of from 1 ~o ` 10~; and :
; ~ y is an integer having a value of from 1 to 100~ ' Subgeneric to (I3 are the compounds represented by the following subgeneric formulas:

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(I) (A) CH2=C~I-Si-R'~
R' R

(I) (B) CH2=c}~coocnH2n-si O R
(I) (C) (R*0)2PCH2CH2 Si-R"
R' : 10 0 R
(I) (~) (R*O)2pcH2cHxcnocnH
R' Subgeneric to ~II) are the conpounds represented by the following subgeneric fQrmulas:

Me Me (II):(A) Me-Si-0-Si-CH-CH2 ~: ~ n O
: Me-Si-0-Si-Me Me Me 20Me~ Me 0 (II) (B) ~!-si-o-si-CH2c~2P (0~*) 2 O O
t r~!-si-o-si -Me Me ~::: Me '' ~ ' ~ -: ` : ~ . - ~ . , :

0 Me Me 0 ,. . . ..
II~ (D) tR*0~2PCH2CH2-Si-0-Si-CH2C~2P(~R )2 O O
(R*0)2PCH2CH2-Si-0-Si-CH2CH2P(OR*)2 0 Me Me 0 Illustrative of suitable silicon compounds one can mention the following: beta-cyanoethyl triethoxy-silane, gamma-mercaptopropyl triethoxysilane, gamma-aminopropyl triethoxysilane, die~hoxyphosphorylethyl : 10 methyl diethoxysilane, vinyl triethoxysilane, vinyl trimethoxysilane, vinvl triacetoxysilane, gamma-meth-acryloxypropyl trimethoxysilane, diethoxyphosphorylethyl heptanethyl cyclotetrasiloxane, trimethyl silyl terminated copolymer havlng dimethylsiloxy and methylvinylsiloxy units in the molecule, beta-cyanoethyl trimethylsilane, : gamma-(Z-aminopropyl triethoxysilane, S-beta(2-mercapto-ethyl) mercaptoethyl triethoxysilane, beta-mercapto-ethyl triethoxys~ilane, vinyl methyl diethoxysilane, vinyl methyl di(trimethylsiloxy~silane, tetramethyl divinyl . 20 disiloxane, heptamethvl vinyl cyclotetrasiloxane, 1,3,5,7-te~ramethyl 1,3,5,7-tetravinyl cyclotetrasiloxane, di-ethoxyphosphoryl~ethyl methyl diethoxysilane, diethoxy-~ -phosphorylisopropyl triethoxysilane, diethoxyphosphoryl-:~: : ethyl methy:L dî(trimethylsiloxy)silane, heptamethyl di-: ethoxyphosphorylethyl cyclotetrasilox~ane~ 1,3,5,7-:
tetramethyl l,::3,5,7-tetra(diethoxyphosphorylethyl)cyclo- ~:
: tetrasiloxane, 1,1,3,3-tetramethyl-1,3-di(diethoxy-:phosphorylet~yl)~di~siIoxane~ ; :

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In a typical reaction, the prescribed amounts of dicarboxylic acid compounds, diols, modifiers and catalysts are charged to the reactorO The reaction mixture is then heated in an inert gas atmosphere at a temperature of from 180C. to ~10C. to effect the initial esteriication or transesterification. There-after, any excess glycol is removed and the transester ification is completed by heating the reaction mixture at a temperature of from about 225~C. to about 235Co The second stage polycon~ensation reaction is then carried out by heating the reaction mixture at a temperature of from about 225C. to about 325C. under a reduced pressure of from about 0.1 mm. to about 20 mmO of mercury, preferably below about 1 mm. The use of the catalyst complexes or mixtures of this invention has often resulted in shorter overall reaction periods and decreased formation of glYcol dimer, e.g~ diethylene glycolO
The following examples serve to further illustrate the invention.
PREPARATION OF COORDINATI~N e XES
Example 1 A coordination complex was produced by preparing a solution of l9 grams of titanium tetrachloride in 60 ml.
of dry benzene in a reaction flask and then adding thereto over a 30 minutes period ?9 . 8 grams of diethoxyphosphoryl- ~
ethyl methyl diethoxysilane. The reaction was exothermic -and a temperature of 60C. was reached. It was stirred for on~ hour without temperature control and then the benzene was~distilled in vacuo. The 1:1 molar ratio coordination complex was an oilv liquid that weighed 48.8 .: : ~ -10. - :

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grams. Microanalysis without further purificatlon showed 28.08% Cl and 5.9~% P.

A solution of 4.75 grams o titanium tetra-chloride in 6~ ml. of dry ben;zene was prepared in a reactor. There was added thereto over a 30 minutes period 10.8~ grams of cyanoethyl triethoxysilane with agitation at 25C, The reaction was exothermic. After stirring at 25C. for an additional hour the benzene was distilled in vacuo. The 1:2 molar ratio coordination complex was a yellow, oily liquid that weighed 15.6 grams. Microanalysis without further purification showed 21.20% Cll 9.11% Si, 4.27% 21 and 8.77% Ti.
Example 3 A mixture of 4.56 grams of antimony trichloride and 36 grams of dry benzene was prepared in a reactorO
To this mixture there was added at 25C. over a 30 minutes - period 41~8 grar~s oif diethoxyphosphorylethyl methyl di-ethoxysilane. The reaction was exothermic. After stirring for an additional hour the benæene was removed in vacuo.
The 1: 7 molar ratio coordination complex was an oily liquid that weighed 46.4 grams.

A solution of 6.5 grams of titanium ~etra-chloride in 30 ml. of dry benzene was slowly added to a stirred solution of 9.7 g. of diethoxyphosphorylethy}
methyl diethc~xvsilane in 30 rnl. of drv benæene. An exother~ic reaction occurred and after standing for one hour the mixture was vacuum stripped at 30C. The 1:1 molar ratio coordination complex was recovered as a residual red oil wei~hing 16.2 grams. ~ 1.4 grams portion of this co7nplex was added to l.~ grams of e~hylene glvcol at room tenperature and the mixture was stirred until it became a homogeneous solution.
Example 5 A solution of 1~.7 gra~s of ge~manium tetrachloride in 25 ml. of dry benæene was added over a period of 30 minutes to 22.1 grams of gamma-a~ino-propyl triethoxysilane. An exotherMic reaction was observed. After stirring one hour without temperature control the benæene was distilled in vacuo. The 1:2 molar ratio complex was a white crvstalline material weighing 33.2 grans.
- Examnle_~
To a solution of 32.8 grams of diethoxy-phosphorylethYl triethoxvsilane in 50 ml. of dry benzene there was added a suspension o 11.66 grams of zirconiun tetrachloride in 30 ml. of dry benzene, An exothermic reaction was observed, The mixture was stirred for one hour without tempera~ure control after completion of the addition, filtered and stripped in vacuo. A colorless, odorless, oily 1:2 molar ratio coordination complex was obtained as a residue product; i~ wei~hed ~3.~ grams.
; ~ Exam~
A solution of 13 grams of tin tetrachloride in 30 ml. of anhydrous benzene was slowly added to a solution of 14.99 grams o~ diethoxyphos~horvlethy~ methyl diethoxysilane in 3n ml. of dry benzene.~ An exo~hermic reaction was obaerved. After standing at room temperature for 20 hours the benzene wa~ distilled in vacuo. The 1:1 12.

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l~h72 molar ratio coordination complex was obtalned as a vellow oil weighing 2~ ~ramsc Example 8 A solution of 9.5 ~ram3 of titanium tetra-chloride in 30 ml. of dry benzene was added slowly to a solution of 22.4 grams of beta-mercaptoethyl triethoxy-silane in 50 ml. of dry ben2ene. An exothermic reaction was observed. After standing for 30 minutes the benzene was distilled in ~7acuo. The 1:2 ~olar ratio coordination complex, weighing 32.1 grams, was recovered as an orange, oily residue produc~.
In a similar manner the coordination complexes can be produced using æinc chloride, lead chloride or bismuth chloride in place of the titanium tetrachloride.
Example ~
(A~ a mixture of 39.8 g. of dimethyl terephthal-ate, 34.1 grams of ethylene glyeol, 0.0167 gram of the 1.1 coordination comPlex catalyst initially produced in Example 4 without addition of ethylene glycol and 0.0192 20 gram of zinc acetate dihydrate was heated at 178 to 186~C.
for 3 hours under argonO During this ~irst stage trans-estarification reaction methanol was distilled from the reactor. The temperature was raised to about 230C. and maintained for one hour to complete the transesterification.
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Thereafter the temperature was raised ~o about 280C.
while the pressure was reduced to below 1 mm. of mercury and the second stage polycondensation reaction was carried out. During the polycondensation, samples of the polyester were removed at various times and intri~sic viscositv determined. The reaction was terminated when the intrinsic ' :: ~

viscosity was 0.57, a typical value for conmercially acceptable polyesters, and the time required was recorded as the polycondensation time (the ~ime from reaching 1 mm. of mercury pressure to when the polyester has an intrinsic viscosity of 0~57)O In this example the polycondensation time was 40 minutesO The intrlnsic viscosity determinations reported in this application were obtained by preparing a solution o~ 0.5 weight per-cent of the polyester in 0-chlorophenol and measuring its viscosity at 25C. in an Ubbelohde viscometer.
(B) For comparison purposes, the polvester was produced using 39.4 grams of dime~hyl terephthalate and 32.? grams of ethvlene glycol under temperature and pressure conditions similar to those described in Part A, supra. However, the catalyst used was the conventional catalyst, namely, 0.0179 gram of zinc acetate dihydrate as transesteriication catalyst and 0.003 gram of - antimony oxide as condensation catalystO In this instance the polycondPnsation time was 75 minutes.
(C) In another reaction under the same reaction conditions but diferent catalyst concentrations than those stated in Part B, the polyester was produced using 0.0172 gram o~ zinc acetat~3 dihydrate and 0.0186 gram of antimony oxide. In this instance the polycondensation time was 60 minutes.
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0ne o~ the undesirable side reactions during the polyesterification reaction is the ~ormation of di-ethylene glycol. It is undesirable for at least two reasons, it is a by-product that cannot be recycled per se 14.

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and it copolymerizes. Further, if too much of the diethylene glycol formed reacts in the condensation reaction it results in polyesters having lower melting points than desired, In this example it is shown that less diethylene glycol is produced using the coordination complexes of our invention as condensation catalyst.
(A) A mixture of 44.9 grams of dimethyl tere-phthalate, 35.3 grams of ethylene glycol and 0.~177 gram of the 1:1 coordination catalyst of Example 1 was reacted at 174 to 190C. for 3 hours under argon and then at about 230C. for one hour to complete the transesterifi-cation. Thereafter the polycondensation was carried out at 276 to 288C. at a pressure below 1 mm. of mercury for a polycondensation time of 40 minutes. The polyester was white and had an intrinsic viScosity of 0.57.
A portion of the polyester was hydrolyzed and the amount of diethylene gl~col in the polyester was determined by gas chromatographic analysisO The analysis indicated that 0.8 weight percent of the ethylene glycol that had dimerized to diethylene glycol had polycondensed.
(B) Following the same procedure described in , `~ Part A, but using 0.0186 gram of zinc acetate dihydrate and 0.02 gram~of antimony oxide, a polyester having the same viscosity was obtained from an initia~ charge of ~ 39.5 grams of dimethyl tetephthalate and 32~8 grams of - ~ ; ethylene gl~col after a polycondensation time o~ 75 minutes.
Analysis of a portion of the polyester of this run (B)~indicated that t~e polyester contained 1.81 weight

3~ percent of diethylene glycol; an amount 2O25 times the ~ amount~present in Part A, supra.
: ::: ~ ' ' lS o Exam~le 11 The effect of a dyeability modifier on fiber color was examined in poly~erizations using our novel co-ordination complexes and the prior conventional catalysts, (A) Following the procedure described in Example 9, a mixture of 735.,8 grams of dimethvl tere-phthalate, 534.2 gra~qs of ethylene glycol, 0.2663 gram of zinc acetate dihydrate and 0.2622 gram of the 1:7 coordination complex catalyst of Example 3 was reacted to produce 605 grams of a polyester having an intrinsic viscosity of 0.5. The unmodified poly(ethylene tere-phthalate was very light yellow in colorO
(B) A portion of the polyester of Part A was modified with 5 weight percent of poly[isopropyliminobis-~trimet~ylene)succinate~, a dyeability modiier. The modifier was added to the molten mass in the extruder of the spinnerette at 280Co The modified polyester showed no color change after 30 minutes ajt that temperature in the extruder.
(C) The procedure of Part A was repeated using 736.4 grams of dimethyl terephthalate and 53302 grams of ethylene glycol and a conventional catalyst system of 0.2711 gram o~ zinc acetate dihydrate and 0.2726 gram o~
;~ antimony oxide to produce S41 grams of a white un-modified polyester.
~D) The procedure o Part B was repeated using the polyester of Part C0 The modified polyester had changed to a grey color.
~te spinning procedure used to produce fibers from the four mixtures,~ A to D above, is set forth below.

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'7 The difference between A and C and B and D being the addition of the dyeability modifier to B and ~ as indicated in Bo The polyester was ground to a powder and vacuum dried for 24 hours before spinning. The molten polyester resin was forced through a sand-bed filter at 290C. to remove gel particles and then extruded through a spinnerette having 30 holes, each 0.02 inch in diameter at a takeup velocity of 550 feet per minute. The tow was stretched by heating over a hot shoe and a heated pin at 95C, ~he stretch ratio was about 4.5:1. In B and D
the dyeability modifier was added as indicated.
The fibers had the following properties:

Elongation Tenacity Part Color Denier at Break,% __~L~ _ (A) ~ite 116 9.4 49 (B) ~ite 127 17.0 3.5 (C) White 111 8.0 4~3 (D) Grey 120 14.0 3.6 The data shows that the ~odified polyester (B) ; produced with the metal ~oordination complex catalysts of ; ~ this invention was of better quality and stability, white vs. grey,than was the modified polyest~r (D) produced using the conven~ional catalyst system.
Examele 12 Following the p~rocedure similar to that described in~EXardple 9, a mixture of 50.1 grams of dimethyl terephthalate~, 42.7 grams of ethylene glycol, 0.0163 gram of zinc acetate dihydrate and 0.048 gram of the catalyst solution of Example 4 was reacted. The .
~ ~ ~ 170 '7 polycondensation time required to produce a white polyester having an intrinsic viscosity of 0.57 was only 24 minutes.
In Part A of Example 9, which used the co-ordination complex catalyst of Example 1, the same viscosity was achieved after a polycondensation time of : 40 minutes. The coordination complex of Example 1 was not pretreated with ethylene glycol as was a por~ion of the coordination complex of Example 4. The data shows that pretreatment increased the activity and only 60% as much time (24 minutes) was required in Rxample 12 to produce a polyester having the same viscosity.
In Part C of Example 9, which used the conven tional zinc acetate-antimony oxide catalyst, the sa~e viscosity was achieved ater a polycondensation time of 60 minutes. The data shows that the ethylene glycol ;; pretreated catalyst solution of Example 4 increased the activity and only 40% as much time (24 minutes) was required to produce a polyester of the same viscosity.
Exam~le 13 .
Following the procedure similar to that described in Example 9, a mixture of 39.7 grams of di-methyl terephthalate, 32.5 grams of ethylene glycol, 0.0181 gram;of zinc acetate dihydrate and 0~0195 gram o the coordination cQmp}ex catalyst o~ Example S was reacted. ~e polycondensation tirne required to produce a white polyester~having an intrinsic visco~ity of 0.57 was 30 minutes.
Fallowing the same procedure, a larger batch was prepared using 736 grams of dimethyl terephthalate, 542 gFans of ethylene glycol, 0.2747 gram of zinc 18.

'7 1~672 acetate dih~ydrate and 0.303 gram of the same germanium coordination complex, 542 grams of e-thylene glycol. The polyester was extruded to fiber-Eo~n as set forth in Example ll. The fibers had a denier of 126, an elongation at breal; of 16.1% and a tenacity of 3,99 g/d.
Example 14 Following the procedure of Example 9, a mixture of 73h grans of dimeth~l terephthalate, 542.~
grams of ethylene glycol, 0.27 gram of zinc acetate di-hydrate and 0.23 gram of the coordination complexcatalyst of Example 7 was reacted. The polyester was : white and had an intrinsic viscosity of 0.55. Fibers were produced as described in Example 11. The fibers had a denier of 101, an elongation at break o 9.7% and a tenacity of 4.8 g/d.
Example 15 Following the procedure of Example ~, a -: mixture of 38.8 grams of dimethyl terephthalate, 31.2 grams of ethylene glycol, 0.012 gram of zinc acetate and 0.02 gram of the coordination complex of Example 6 was reacted to produce a pol~ester having an average nolecular weight of about 12 J 500 after a polycondensation period of about 90 minutes.

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Claims

WHAT WE CLAIM IS:

1. In a process for the manufacture of solid fiber-forming polyesters or copolyesters of dicarboxylic acid compounds and aliphatic glycols in the presence of catalysts, the improvement which comprises using as poly-esterification catalyst a coordination complex of (A) and (B), wherein:
(A) is a metal halide of a metal selected from the group consisting of titanium, zirconium, zinc, germanium, tin, lead, antimony and bismuth; and (B) is a silicon compound selected from the group consisting of:

(I) (II) (III) or (IV) QCH2CH25iR3**

20.

wherein W is CH2=CX- or (R*O)2PCH2CHX- ;

X is hydrogen or methyl and is methyl only when m is one;
R* is alkyl or haloalkyl having from 1 to 4 carbon atoms;
R** is methyl, ethyl, butyl, acetoxy, methoxy, ethoxy or butoxy;
R is methyl, ethyl, butyl, methoxy, ethoxy, butoxy or trimethvlsiloxy;
R' is methyl, methoxy, ethoxy, butoxy or trimethylsiloxy;
R" is methoxy, ethoxy, butoxy, trimethylsiloxy or vinyldimethylsiloxy;
R"' is methyl, ethyl, butyl or trimetheylsiloxy;
Me is methyl;
Z is methyl or W;
Q is an NH2CH2- , NH2CH2CH2NHCH2- , NC-, HS- or HSCH2CH2S- group;
n is an integer having a value of from 2 to 5;
m is an integer having a value of zero or one;
x is an integer having a value of from 1 to 100; and y is an integer having a value of from 1 to 100;
wherein the mole ratio of A:B in said coordination complex is from 1:1 to 1:7.

21.

2. A process as claimed in claim 1, wherein silicon compound (B) is a compound of the general formula:

wherein W, R, R', R", n and m are as defined in claim lo 3. A process as claimed in claim 1, wherein silicon compound (B) is a compound of the general formula:

wherein Me, W and Z are as defined in claim 1.

4. A process as claimed in claim 1, wherein silicon compound (B) is a compound of the general formula:

wherein Me, W, R"', x and y are as defined in claim 1.

5. A process as claimed in claim 1, wherein silicon compound (B) is a compound of the general formula:

22.

QCH2CH2SiR3**
wherein Q and R** are as defined in claim 1.

6. A process as claimed in claim 1, wherein the silicon compound (B) is diethoxyphosphorylethyl methyl diethoxysilane.

7. A process as claimed in claim 1, wherein the silicon compound (B) is 3-aminopropyl triethoxysilane.

8. A process as claimed in claim 1, wherein the silicon compound (B) is 2-cyanoethyl triethoxysilane.

9. A process as claimed in claim 1, wherein the silicon compound (B) is 2-mercaptoethyl triethoxy-silane.

10, A process as claimed in claim 1, wherein said polyesterification catalyst is a coordination complex of titanium tetrachloride and diethoxyphosphorylethyl methyl diethoxysilane.

11. A process as claimed in claim 1, wherein said polyesterification catalyst is a coordination complex of titanium tetrachloride and 2-cyanoethyl triethoxysilane.

12. A process as claimed in claim 1, wherein said polyesterification catalyst is a coordination complex of antimony trichloride and diethoxyphosphorylethyl methyl dietheoxysilane.

1:3. A process as claimed in claim 1, wherein said polyesterification catalyst is a coordination complex of germanium tetrachloride and 3-aminopropyl triethoxy-silane.

23.

14. A process as claimed in claim 1, wherein said polyesterification catalyst is a coordination complex of zirconium tetrachloride and diethoxyphosphorylethyl methyl diethoxysilane.

15. A process as claimed in claim 1, wherein said polyesterification catalyst is a coordination complex of tin tetrachloride and diethoxyphosphorylethyl methyl diethoxysilane.

16. A coordination complex of:
(A) a metal halide of a metal selected from the group consisting of titanium, zirconium zinc, germanium, tin, lead, antimony and bismuth; and (B) a silicon compound selected from the group consisting of:
(I) (II) (III) 24.

(IV) QCH2CH2SiR3**
wherein W is CH2=CX- or (R*O)2PCH2CHX- ;
O

X is hydrogen or methyl and is methyl only when m is one;
R* is alkyl or haloalkyl having from 1 to 4 carbon atoms;
R** is methyl, ethyl, butyl, methoxy, ethoxy or butoxy;
R is methyl, ethyl, butyl, methoxy, ethoxy, butoxy or trimethylsiloxy;
R' is methyl, methoxy, ethoxy, butoxy or trimethylsiloxy;
R" is methoxy, ethoxy, butoxy, trimethylsiloxy or vinyldimethylsiloxy;
R"' is methyl ethyl, butyl or trimethylsilyl;
Me is methyl;
Z is methyl or W;

Q is NC-, HS- or HSCH2CH2S- group;
n is an integer having a value of from 2 to 5;
m is an integer having a value of zero or one;
is an integer having a value of from 1 to 100;
and y is an integer having a value of from 1 to 100;
wherein the mole ratio of A:B in said coordination complex is from 1:1 to 1.:7.

25.

17. A coordination complex as claimed in claim 16, wherein silicon compound (B) is a compound of the general formula:

wherein W, R, R', R", n and m are as defined in claim 1.

18. A coordination complex as claimed in claim 16, wherein silicon compound (B) is a compound of the general formula:

wherein Me, W and Z are as defined in claim 1.

19. A coordination complex as claimed in claim 16, wherein silicon compound (B) is a compound of the general formula:

wherein Me, W, R"', x and y are as defined in claim 1.

26.

20. A coordination complex as claimed in claim 16, wherein silicon compound (B) is a compound of the general formula:
QCH2CH2SiR3**
wherein Q and R** are as defined in claim 1.

21. A coordination complex as claimed in claim 16, wherein the silicon compound (B) is diethoxyphosphorylethyl methyl diethoxysilane.

22. A coordination complex as claimed in claim 16, wherein the silicon compound (B) is 2-cyanoethyl triethoxy-silane.

23. A coordination complex as claimed in claim 16, wherein the silicon compound (B) is 2-mercaptoethyl triethoxysilane.

24. A coordination complex as claimed in claim 16 of titanium tetrachloride and diethoxyphosphorylethyl methyl diethoxysilane.

25. A coordination complex as claimed in claim 16 of titanium tetrachloride and 2-cyanoethyl triethoxysilane.

26. A coordination complex as claimed in claim 16 of antimony trichloride and diethoxyphosphorylethyl methyl diethoxysilane.

27.

27. A coordination complex as claimed in claim 16 of zirconium tetrachloride and diethoxyphosphorylethyl methyl diethoxysilane.

28. A coordination complex as claimed in claim 16 of tin tetrachloride and diethoxyphosphorylethyl methyl diethoxysilane.

28.